Alkylation-recycling of alkylate product stream free of inert gases



May 25, 1948. A. R. sYDNoR, .JR

yALKYLATION-RECYCLING OF ALKYLATE PRODUCT STREAM FREE OF* INERT GASES Filed June 19, 19'45 mazmvLnq-wwuowag @u VT@ OJ iv k oz, $7 ma, um. Q 2 ad me 2J! m.. mw i O daJOOUJ d d d N .w m W I+ j, i V N NOPU m ,2 w. m* s (i uuJrrmmf, E. 2 N. Y@ AwvM/MJONN Y mw MZMPDOOW. mJui/Omdw uns( uzrnaom.

roman shleq 12.5qdnog3Jr. Bru/anto? v f Cltborrzeq Patented May 25, v1948 ALKYLATION-RECYCLING OF PRODUCT STREAM FREE GASES Ashley ALKYLATE OF INERT R. SydnonJrr., Fanwood, N. J., assignor to Standard Oil Development Company, a corporation of Delaware Application June 19, 1945, serial No. 600,247

` claims. (o1. 26o-4683A) The novel features of my invention are disclosed in the following specification and claims considered in connection with the accompanying drawing.

The object of my invention is to alkylate iso paramn with olens in the presence of a suitable catalystI under conditions which will insure maximum yields of high quality product. y

Another object of my invention is to alkylate an isoparain with an olefin containing not more than three carbon atoms. I

I have discovered that in alkylating an isoparain with an olefin it is preferable to operate under conditions such that the normally gaseous constituents (including non-condensable gases, such as hydrogen) are maintained in liquid phase in the reaction zone; and this result is accomplished not only by operating under superatmospheric pressure but by recycling sui'lieient liquid product to the reaction Zone, so that normally gaseous materials may be dissolved in the liquid phase, that is, providing in the reaction Zone merely liquid phases and not a mixture of liquid and gas phases. The solution of normally gaseous materials is also further aided by a careful fractional distillation of the crude product to remove non-condensable gases such as hydrogen, and also to remove inert gases such as methane, ethane, and propane, before a'portion of the crude product is recycled to the reaction zone.

In the accompanying drawing I have. shown diagrammatically an apparatus layout in which a preferred modification of my invention may be carried into practical effect.

In the alkylation of isobutane with olefins, using an AlCls-hydrocarbon complex catalyst, the reaction isgenerally carried out in a closed vessel at about 50 F. to 150 F. and 250 to 3,00 pounds per square inch gauge pressure. Good mixing of reactants and catalyst is maintained Aby means of propeller stirrers disposed in the reaction zone, by recycling the contents of the reactor through jets, also located in the reaction zone, by means of an external pump, etc. Good results are obtained by maintaining a large excess of isoparairln, say at least 100 mols of isoparain per mol of olen in the reaction zone. These facts were known prior to my invention. I have now found that improved results are achieved by these means, as long as all the gaseous constitu ents are maintained in the liquid phase. When,

however, the olens as fed are diluted with inert, non-condensable gases, such as hydrogen and methane, unless the precautions I have noted above are observed, both liquid and gas phases exist in the reactor. The presence of the dissimilar phases makes more diicult the problem of securing adequate mixing, which is necessary to insure that good yields and product quality are secured.

Referring in detail to the drawing, I represents a reactor and 'I and 8, respectively, represent fresh isobutane and olefin feed lines. In the drawing, these discharge the isobutane and olen (e. g. ethylene or propylene). into isobutane recycle line 9, after which the mixture passes via lines IIb and Ile `through an orifice mixer I2 and thence flows `via line 13a into a jet mixer 25 disposed Within reactor I. The catalyst, an aluminum chloride-hydrocarbon complex, is formed by thereaction of anhydrous aluminum chloride with isoparaflins, such as trimethyl pentanes, etc., convenient sources of said isoparaiiins being commercial sulfuric acid alkylate, in particular the CF1-Cs cut from the alkylate made in this sulfuric acid process. The complex may be preformed outside the system shown in the drawing, using hydrogen chloride, methyl chloride (1 to 5 volume per cent of the isoparafn) as promoter at atmospheric pressure and temperatures above about 150*7 F. during a period of several hours (say 6 to 8) and then charged to the alkylation unit with the fresh isobutane or it may be formed in situ by the addition of anhydrous aluminum chloride directly to the alleylation reactor containing an isoparafiin and formed therein under the same conditions. In general, the initial catalyst is preformed and the make-up catalyst is formed in situ by periodic additions of anhydrous aluminum chloride to the reactor in solution in the fresh isobutane stream 1. The olens, isobutane, and aluminum chloridahydrocarbon complex mix with and Contact each other at a temperature of F. to 150 F. in the reactor I under a gauge pressure of 250 to 300 pounds per square inch for a sufficient period of time to eiect the desired conversion. Thereafter, a crude product is withdrawn from the reactor through line I4, discharged into settler 2 wherein any aluminum chloride-hydrocarbon complex carried over vby entrainment separates out and is returned to the reactor via line I5. `As previously stated, the upper liquid phase is withdrawn from settler 2 through line I5 and. the major portion of the upper liquid phase, say to 98% is recycled to the reactor I through line i3 and i3d and the jets 25 in order to provide mixing, The remaining portion of the product is discharged via line Il into a depropanizer tower 3 from which the residue gas, which.r contains inert gas from feed, such as hydrogen, methane, ethane, and propane, and any unreacted ethylene and propylene is taken ofi overhead through line i8, while the bottoms may be recycled via line I0 to reactor I, at least in part, the remainder passing via line I3 into a de-isobutanizer 4 from which unreacted isobutane is withdrawn overhead through line 9 and recycled to the reaction zone. The bottoms in tower 4 are withdrawn through line 20 and discharged intoL tower 5 .wherein normal. butane'.

is withdrawnithrough line 2|, Whilethe bottoms are Withdrawn through line 22 and discharged into a finishing still y6 from which a fraction of.' the alkylate suitable for inclusion in aviation. gasoline is taken off overheadfthrough lin'e.23'v

and a heavier residual alkylate is taken ofi through line 24.

Spent catalyst is withdrawl'-peri'odically-fromf` the system via line Ia.

I have made test runs to determine the utility of my invention and I have secured dataY which" show that when a gaseous olefin such as ethylene or propylene is reacted with liquid isoparaffins in the presence of the A1013 catalyst previoush7 Olen Feed Composition:

Hydrogen, MolyPerCentL. 9

Methane" 0 36 Ethylene. 65 18 Propylene 30 10 Propane 2r l 22 Mol Ratio of Isobuta'ne to Qlefins'in. Total Fee d 5.7/1 5.6/1 Oleln Feed Rate, Gram Mols Ethylene plus Prop Y ylene per Hour 9. 4 6, 8 Reactor Hydrocarbon Recircula n'Rate (a meas.

Vure of mixing), Gals. per Hour 95 90 Reactor Volume, Liters.` 22 22 .l et Diameter, Inches 0.138 O, 138 .Tet Pressure Drop, lbs/sq. in 10 10 Reactory Pressure, lbs/sq. in'.' Gauge Pre 275' 275 Reactor Temperature,` F-- 130 1 130 Per Cent Ethylene Reacted.. 96. 5 92. 7 Per .Cent Propylene Reacte'd. 994` 99+ Yield ofvAlkylate, Based-on Input. Olefins; Welght L Y Per C 262 244 To' recapitu-late briefly, my invention has to do withl improvements 4in the .alkylation of olei'lns, such as ethyleneandpropylene,. .Wil-.han isoparain, such asisobutane or isopentane, conducted in thev presence of a: liquidcatalyst such as :the aluminum chloride'-hydrocarbonV complex. The-.main pointl ofv the-.inventionisthat only liquidphases"Y are maintained in the Areaction zone, and this is accomplished byerecycling sucient product, from'vvhichhydrogen,y methane,

ethane; and -propanefhave been Vremoved by. dis-V tillation, to dissolve and 'maintain .fthenormally gaseous constituents Ain the liquid-phase. B-yso operating, I improve the ryieldof alkylate and also improve the quality' ofthe alkylate..y

While -I have described inldetail operations in which the catalystis ian aluminum chloridehydrocarbon complex, it'is -tobeY understood. that many improvements are applicableto any liquid catalyst, adapted-'to :effect :the :alkylation of isoparaiiinswith olelns, iny particular,"r those` olens containingl-not more than"three`carbon atoms in the molecule. With respect to the aluminum 'chloride hydrocarbon complex, l? have found .that goodresults are obtained by using a catalyst which. contains from 35'to 40 per cent hydrocarbon in the complex composition. In physical appearance the hydrocarbon complex is a brown, mobile liquid. vhavinga specific gravity of around "1.2;- but other-forms of this and other liquid catalysts mentioned may be used.

VNumerous Vmodifications of my invention following within the spirit thereof may be made by those Who are familiar with this art.

'What I claim is: i

1. In the alkylatiorrof an.isoparafirrwith.r a C2 to 'Ce olefin and inixecwithv Ainertfgfas.`in'clud` ing hydrogen in the presence of 'aliquid'cataly'st at an elevated alkylation temperature andfunder suiiicient -pressure to maintain*y the isoparafiin the'liquid phase, theimprovemen'ts i'fzhich.com-V prise maintaining the olefin` dissolvedin. a. liquidi phase whileit is resident in the'reaction vz'onefior a suicient time period toeiect alkylation ofthe isoparailn in liquid phase;v dissolving.' inf the liquid phase the inert gas, including hydrogen; methane, ethane and propane, present inthe reaction zone; removing from "said reaction-zone a liquid alkylate'product together With'umeacted liquid isoparafln containing dissolvedgas th'ere- Y in, passing this alkylate stream to -a separa-trony zone and efiectingr separationV betWeenthe-'ca'taelyst and said alkylate stre'arnfrecycling a portion -of said alkylate stream directly to said reaction zone, introducing the remaining portion'- of-sfaid alkylate stream intoa separation vzonevvhere'in said dissolvedinert gases, including hydrogen;

are removed from this latteralkylatestream? Vrejcycling a portion of Ythis latter alkylate vstream free of inert gases to said reaction zonawhreb'y the amount of said inert gases present ini-said reaction zone is diminished, and handling' the remaining portion of this'latter allyla-te stream freer of :inert gases in amanner to segregatefV theV alkylated product.'

2.7The method or mimi, in whicn'lth'efisoparain alkylated isj isobutane nand the olefin-is ethylene. u v

3. The method of Vclaim 1,` in which the isoparaiiin alkylated is isobutane and the olen is propylene.

4. The method set forth in claim f1, in which the catalyst is an aluminum'chloride hydrocarbon complexcontaining 35-40 Weight percent-hy- 5. The methodv set iorthin claim 1,'`inwhich the alkylation temperature is Within the-'range of'from about 50 to 150 F. and the superatL mospheric pressure maintained in the reaction zone is in the range from 250-300pou-1rds per square inch gauge. p Y

ASHLEY R. sYDNOagJie REFERENCES CITED." I Thefollowing references are-.of record`in the fileof this patent:v

UNITED. STATES PATENTS Number Name. Date L 2,354,652 Carmody et al. Aug.'f1,` 19'44 2,363,264 Rosen Nov. 2 1; 19144 2,399,093

Bonnell et .al,. Apri 23,' 1946 

